Antifouling composition, treatment device, treatment method, and treated article

ABSTRACT

A surface-treating agent including a fluorine-containing compound having a carbon-carbon unsaturated bond at its molecular terminal as a group of —Y-A wherein Y is a single bond, an oxygen atom or a divalent organic group, and A is —CH═CH2 or —C≡CH, which is able to form a layer having higher alkaline resistance.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/JP2015/070865 filed Jul. 22, 2015, claiming priority based onJapanese Patent Application Nos. 2014-161771 filed Aug. 7, 2014 and2015-081249 filed Apr. 10, 2015, the contents of all of which areincorporated herein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a surface-treating agent or anantifouling composition comprising a fluorine-containing compound havinga carbon-carbon unsaturated bond at its molecular terminal.

BACKGROUND ART

A certain fluorine-containing silane compound is known to be able toprovide excellent water-repellency, oil-repellency, antifoulingproperty, or the like when it is used in a surface treatment of a basematerial. A layer (hereinafter, referred to as a “surface-treatinglayer”) formed from a surface-treating agent comprising afluorine-containing silane compound is applied to various base materialssuch as a glass, a plastic, a fiber and a building material as aso-called functional thin film.

As such fluorine-containing silane compound, a perfluoropolyether groupcontaining silane compound which has a perfluoropolyether group in itsmolecular main chain and a hydrolyzable group bonding to a Si atom inits molecular terminal or terminal portion is known (see PatentDocuments 1 and 2). When the surface-treating agent comprising theperfluoropolyether group containing silane compound is applied on a basematerial, a reaction of the hydrolyzable group bonding to a Si atombetween the compound and the base material and between the compounds isoccurred to form the surface-treating layer.

PRIOR ART DOCUMENT Patent Document

Patent Document 1: JP 2008-534696 A

Patent Document 2: International Publication No. 97/07155

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

However, since the surface-treating layer as described above is bondedto the base material by —Si—O—Si— bond, there is a possibility that thebond is cleaved and the durability is decreased under an alkalineenvironment, particularly a strong alkaline environment, for examplewhen perspiration is contacted to the base material.

Therefore, an object of the present invention is to provide a novelsurface-treating agent which is able to form a layer having higheralkali resistance.

Means to Solve the Problem

As a result of intensively studying, the inventors of the presentinvention have found that the surface-treating layer having higheralkali resistance can be formed by introducing a carbon-carbonunsaturated bond into a molecular terminal of the fluorine-containingcompound and reacting it with a Si—H bond or a C—H bond of the basematerial to bond between the base material and the surface-treatinglayer by a Si—C bond or a C—C bond, and the inventors have reached thepresent invention.

Therefore, according to the first aspect of the present invention, thereis provided a surface-treating agent comprising a fluorine-containingcompound having a carbon-carbon unsaturated bond at its molecularterminal as a group of —Y-A wherein Y is a single bond, an oxygen atomor a divalent organic group, and A is —CH═CH₂ or —C≡CH.

According to the second aspect of the present invention, there isprovided an article comprising a base material and a layer which isformed on a surface of the base material from the surface-treating agentof the present invention.

According to the third aspect of the present invention, there isprovided a method for forming a surface-treating layer on a surface of abase material comprising the steps of:

performing a pretreatment of the base material so as to form a bindingsite with a fluorine-containing compound having a carbon-carbonunsaturated bond at its molecular terminal on the surface of the basematerial; and

applying the surface-treating agent according of the present inventionto the base material subjected to the pretreatment to form thesurface-treating layer on the surface of the base material.

According to the fourth aspect of the present invention, there isprovided a surface-treating layer forming apparatus for forming asurface-treating layer on a surface of the base material comprising:

a pretreatment unit for performing a pretreatment of the base materialto form a binding site with a fluorine-containing compound having acarbon-carbon unsaturated bond at its molecular terminal on the surfaceof the base material, and

a surface-treating layer forming unit for applying the surface-treatingagent of the present invention to the base material subjected to thepretreatment to form the surface-treating layer on the surface of thebase material.

According to the fifth aspect of the present invention, there isprovided a process for producing an article comprising a base materialand a surface-treating layer coating a surface of the base materialcomprising a step of:

contacting the surface-treating agent of the present invention to thesurface of the base material so that the fluorine-containing compoundhaving a carbon-carbon unsaturated bond at its molecular terminalcontained in the surface-treating agent is reacted with a Si—H part or aC—H part of the surface of the base material to form thesurface-treating layer on the surface of the base material.

Effect of the Invention

According to the surface-treating agent comprising a fluorine-containingcompound having a carbon-carbon unsaturated bond at the molecularterminal of the present invention, the surface-treating layer havinghigh alkali resistance can be formed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram showing one embodiment of a surface-treatinglayer forming apparatus for forming the surface-treating layer on a basematerial.

FIG. 2 is a cross-sectional view schematically showing one embodiment ofthe pretreatment unit 200 in the surface-treating layer formingapparatus shown in FIG. 1.

EMBODIMENTS TO CARRY OUT THE INVENTION

Hereinafter, the surface-treating agent of the present invention will bedescribed.

The “2-10 valent organic group” as used herein represents a 2-10 valentgroup containing a carbon atom. Examples of the 2-10 valent organicgroup include, but are not particularly limited to, a 2-10 valent groupobtained by removing 2-9 hydrogen atoms from a hydrocarbon group. Forexample, examples of the 2-10 valent organic group include, but are notparticularly limited to, a divalent group obtained by removing onehydrogen atom from a hydrocarbon group from a hydrocarbon group.

The “hydrocarbon group” as used herein represents a group containing acarbon atom and a hydrogen atom. Examples of the hydrocarbon groupinclude, but are not particularly limited to, a hydrocarbon group having1-20 carbon atoms which may be substituted by one or more substituents,for example, an aliphatic hydrocarbon group, an aromatic hydrocarbongroup, and the like. The “aliphatic hydrocarbon group” may be straight,branched or cyclic, and may be saturated or unsaturated. The hydrocarbongroup may contain one or more ring structures. It is noted that thehydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl,siloxane, carbonyl, carbonyloxy, or the like at its end or in itsmolecular chain.

As used herein, examples of the substituent of the “hydrocarbon group”include, but are not particularly limited to, for example a halogenatom; and a C₁₋₆ alkyl group, a C₂₋₆ alkenyl group, a C₂₋₆ alkynylgroup, a C₃₋₁₀ cycloalkyl group, a C₃₋₁₀ unsaturated cycloalkyl group, a5-10 membered heterocyclyl group, a 5-10 membered unsaturatedheterocyclyl group, a C₆₋₁₀ aryl group, a 5-10 membered heteroarylgroup, and the like, which may be substituted by one or more halogenatoms.

The present invention provides the surface-treating agent comprising afluorine-containing compound having a carbon-carbon unsaturated bond atits molecular terminal as a group of —Y-A wherein Y is a single bond, anoxygen atom or a divalent organic group, and A is —CH═CH₂ or —C≡CH.

Y is a single bond, an oxygen atom or a divalent organic group. Y ispreferably a single bond, an oxygen atom or —CR¹⁴ ₂—.

R¹⁴ is each independently at each occurrence a hydrogen atom or a loweralkyl group. The lower alkyl group is preferably an alkyl group having1-20 carbon atoms, more preferably an alkyl group having 1-6 carbonatoms, further preferably a methyl group. R¹⁴ is preferably a hydrogenatom.

A is —CH═CH₂ or —C≡CH. A is preferably —CH═CH₂.

In a preferably embodiment, the fluorine-containing compound having acarbon-carbon unsaturated bond at the molecular terminal may be acompound of any of the following formulae (A1), (A2), (B1), (B2), (C1),(C2), (D1) and (D2):

Hereinafter, the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and(D2) described above are described.

Formulae (A1) and (A2):

In the formula, Rf is an alkyl group having 1-16 carbon atoms which maybe substituted by one or more fluorine atoms.

The “alkyl group having 1-16 carbon atoms” in the alkyl having 1-16carbon atoms which may be substituted by one or more fluorine atoms maybe straight or branched, and preferably is a straight or branched alkylgroup having 1-6 carbon atoms, in particular 1-3 carbon atoms, morepreferably a straight alkyl group having 1-3 carbon atoms.

Rf is preferably an alkyl having 1-16 carbon atoms substituted by one ormore fluorine atoms, more preferably a CF₂H—C₁₋₁₅ perfluoroalkylenegroup, more preferably a perfluoroalkyl group having 1-16 carbon atoms.

The perfluoroalkyl group having 1-16 carbon atoms may be straight orbranched, and preferably is a straight or branched perfluoroalkyl grouphaving 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferablya straight perfluoroalkyl group having 1-3 carbon atoms, specifically—CF₃, —CF₂CF₃ or —CF₂CF₂CF₃.

In the formula, PFPE is—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—, and corresponds to aperfluoro(poly)ether group. Here, a, b, c and d are each independently 0or an integer of 1 or more and are not particularly limited as long asthe sum of a, b, c and d is 1 or more. Preferably, a, b, c and d areeach independently an integer of 0 or more and 200 or less, for examplean integer of 1 or more and 200 or less, more preferably eachindependently an integer of 0 or more and 100 or less, for example, aninteger of 1 or more and 100 or less. More preferably, the sum of a, b,c and d is 10 or more, preferably 20 or more, and 200 or less,preferably 100 or less. The occurrence order of the respective repeatingunits in parentheses with the subscript a, b, c or d is not limited inthe formula. Among these repeating units, the —(OC₄F₈)— group may be anyof —(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂CF₂)—, —(OCF₂CF(CF₃)CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—,—(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F₅)CF₂)— and —(OCF₂CF(C₂F₅))—, preferably—(OCF₂CF₂CF₂CF₂)—. The —(OC₃F₆)— group may be any of —(OCF₂CF₂CF₂)—,—(OCF(CF₃)CF₂)— and —(OCF₂CF(CF₃))—, preferably —(OCF₂CF₂CF₂)—. The—(OC₂F₄)— group may be any of —(OCF₂CF₂)— and —(OCF(CF₃))—, preferably—(OCF₂CF₂)—.

In one embodiment, PFPE is —(OC₃F₆)_(b)— wherein b is an integer of 1 ormore and 200 or less, preferably 10 or more and 100 or less, preferably—(OCF₂CF₂CF₂)_(b)— wherein b is as defined above.

In another embodiment, PFPE is—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)— wherein a and b areeach independently an integer of 0 or more, or 1 or more and 30 or less,preferably 0 or more and 10 or less, and c and d are each independentlyan integer of 1 or more and 200 or less, preferably 10 or more and 100or less. The sum of a, b, c and d is 10 or more, preferably 20 or moreand 200 or less, preferably 100 or less. The occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula. Preferably, PFPE is—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)— whereina, b, c and d are as defined above. For example, PFPE may be—(OCF₂CF₂)_(c)—(OCF₂)_(d)— wherein c and d are as defined above.

In another embodiment, PFPE is —(OC₂F₄—R¹⁵)_(n″)—. In the formula, R¹⁵is a group selected from OC₂F₄, OC₃F₆ and OC₄F₈, or a combination of 2or 3 groups independently selected from these groups. Examples of thecombination of 2 or 3 groups independently selected from OC₂F₄, OC₃F₆and OC₄F₈ include, but not particularly limited to, for example,—OC₂F₄OC₃F₆—, —OC₂F₄OC₄F₈—, —OC₃F₆OC₂F₄—, —OC₃F₆OC₃F₆—, —OC₃F₆OC₄F₈—,—OC₄F₈OC₄F₈—, —OC₄F₈OC₃F₆—, —OC₄F₈OC₂F₄—, —OC₂F₄OC₂F₄OC₃F₆—,—OC₂F₄OC₂F₄OC₄F₈—, —OC₂F₄OC₃F₆OC₂F₄—, —OC₂F₄OC₃F₆OC₃F₆—,—OC₂F₄OC₄F₈OC₂F₄—, —OC₃F₆OC₂F₄OC₂F₄—, —OC₃F₆OC₂F₄OC₃F₆—,—OC₃F₆OC₃F₆OC₂F₄—, —OC₄F₈OC₂F₄OC₂F₄—, and the like. n″ is an integer of2-100, preferably an integer of 2-50. In the above-mentioned formula,OC₂F₄, OC₃F₆ and OC₄F₈ may be straight or branched, preferably straight.In this embodiment, PFPE is preferably —(OC₂F₄—OC₃F₆)_(n″)— or—(OC₂F₄—OC₄F₈)_(n″)—.

In the formula, R¹¹ is each independently at each occurrence a hydrogenatom or a halogen atom. The halogen atom is preferably an iodine atom, achlorine atom, a fluorine atom.

In the formula, R¹² is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms.

In the formulae (A1) and (A2), X¹ is each independently a single bond ora 2-10 valent organic group. The X¹ group is recognized to be a linkerwhich connects between a perfluoropolyether moiety (an Rf-PFPE moiety or-PFPE-moiety) providing mainly water-repellency, surface slip propertyand the like and a group having a carbon-carbon unsaturated bond(specifically, the A group or a group containing the A group) providingan ability to bind to a base material in the compound of the formula(A1) and (A2). Therefore, the X¹ group may be any organic group as longas the compound of the formula (A1) and (A2) can stably exist.

In the formula, α is an integer of 1-9, and α′ is an integer of 1-9. αand α′ are determined depending on the valence number of the X¹ group.In the formula (A1), the sum of α and α′ is the valence number of the X¹group. For example, when X¹ is a 10 valent organic group, the sum of αand α′ is 10, for example, α is 9 and α′ is 1, α is 5 and α′ is 5, or αis 1 and α′ is 9. When X¹ is a divalent organic group, α and α′ are 1.In the formula (A2), α is a value obtained by subtracting 1 from thevalence number of the X¹ group.

X¹ is preferably a 2-7 valent, more preferably 2-4 valent, morepreferably a divalent organic group.

Examples of X¹ include, but are not particularly limited to, for examplea divalent group of the following formula:—(R³¹)_(p′)—(X^(a))_(q′)—R³²—wherein:

R³¹ is a single bond, —(CH₂)_(s′)— or an o-, m- or p-phenylene group,preferably —(CH₂)_(s′)—,

R³² is a single bond, —(CH₂)_(t′)— or an o-, m- or p-phenylene group,preferably —(CH₂)_(t′)—,

s′ is an integer of 1-20, preferably an integer of 1-6, more preferablyan integer of 1-3, further more preferably 1 or 2,

t′ is an integer of 1-20, preferably an integer of 2-6, more preferablyan integer of 2-3,

X^(a) is —(X^(b))_(r′)—,

X^(b) is each independently at each occurrence a group selected from thegroup consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—,—CONR³⁴—, —O—CONR³⁴—, —NR³⁴—, —Si(R³³)₂—, —(Si(R³³)₂O)_(m′)—Si(R³³)₂—,and —(CH₂)_(n′)—,

R³³ is each independently at each occurrence a phenyl group, a C₁₋₆alkyl group or a C₁₋₆ alkoxy group, preferably a C₁₋₆ alkyl group, morepreferably a methyl group,

R³⁴ is each independently at each occurrence a hydrogen atom, a phenylgroup or a C₁₋₆ alkyl group (preferably a methyl group),

m′ is each independently an integer of 1-100, preferably an integer of1-20,

n′ is each independently at each occurrence an integer of 1-20,preferably an integer of 1-6, more preferably an integer of 1-3,

r′ is an integer of 1-10, preferably an integer of 1-5, more preferablyan integer of 1-3,

p′ is 0 or 1, and

q′ is 0 or 1,

at least one of p′ and q′ is 1, and the occurrence order of therespective repeating units in parentheses with the subscript p′ or q′ isnot limited in the formula.

Preferably, X¹ may be

a C₁₋₂₀ alkylene group,

—R³¹—X^(c)—R³²—, or

—X^(d)—R³²—

wherein R³¹ and R³² are as defined above.

More preferably, X¹ may be,

a C₁₋₂₀ alkylene group,

—(CH₂)_(s′)—X—,

—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—

—X^(d)—, or

—X^(d)—(CH₂)_(t′)—

wherein s′ and t′ are as defined above.

In the formula, X^(c) is

—O—,

—S—,

—C(O)O—,

—CONR³⁴—,

—O—CONR³⁴—,

—Si(R³³)₂—,

—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,

—O—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,

—CONR³⁴—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,

—CONR³⁴—(CH₂)_(u′)—N(R³⁴)—, or

—CONR³⁴— (o-, m- or p-phenylene)-Si(R³³)₂—

wherein R³³, R³⁴ and m′ are as defined above,

u′ is an integer of 1-20, preferably an integer of 2-6, more preferablyan integer of 2-3. X^(c) is preferably —O—.

In the formula, X^(d) is

—S—,

—C(O)O—,

—CONR³⁴—,

—CONR³⁴—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,—CONR³⁴—(CH₂)_(u′)—N(R³⁴)—, or

—CONR³⁴— (o-, m- or p-phenylene)-Si(R³³)₂—.

More preferably, X¹ may be

a C₁₋₂₀ alkylene group,

—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—, or

—X^(d)—(CH₂)_(t′)—

wherein each symbol is as defined above.

Further, more preferably, X¹ is

a C₁₋₂₀ alkylene group,

—(CH₂)_(s′)—O—(CH₂)_(t′)—,

—(CH₂)_(s′)—Si(R³³)₂—(CH₂)_(t′)—,

—(CH₂)_(s′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—(CH₂)_(t′)—,

—(CH₂)_(s′)—O—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—(CH₂)_(t′)—, or

—(CH₂)_(s′)—O—(CH₂)_(t′)—Si(R³³)₂—(CH₂)_(u′)—Si(R³³)₂—(C_(v)H_(2v))—

wherein each symbol is as defined above, v is an integer of 1-20,preferably an integer of 2-6, more preferably an integer of 2-3.

In the formula, —(C_(v)H_(2v))— may be straight or branched, and may befor example —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)—, or —CH(CH₃)CH₂—.

The above-mentioned X¹ group may be substituted by one or moresubstituents selected from a fluorine atom, a C₁₋₃ alkyl group and aC₁₋₃ fluoroalkyl group (preferably, a C₁₋₃ perfluoroalkyl group).

Specific examples of X¹ include, for example:

—CH₂O(CH₂)₂—,

—CH₂O(CH₂)₃—,

—CH₂O(CH₂)₆—,

—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,

—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,

—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,

—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,

—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,

—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,

—CH₂OCF₂CHFOCF₂—,

—CH₂OCF₂CHFOCF₂CF₂—,

—CH₂OCF₂CHFOCF₂CF₂CF₂—,

—CH₂OCH₂CF₂CF₂OCF₂—,

—CH₂OCH₂CF₂CF₂OCF₂CF₂—,

—CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,

—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,

—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,

—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,

—CH₂OCH₂CHFCF₂OCF₂—,

—CH₂OCH₂CHFCF₂OCF₂CF₂—,

—CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,

—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,

—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,

—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—

—CH₂OCH₂ (CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,

—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,

—(CH₂)₂—,

—(CH₂)₃—,

—(CH₂)₄—,

—(CH₂)₆—,

—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—

—CONH—(CH₂)₃—,

—CON(CH₃)—(CH₂)₃—,

—CON(Ph)-(CH₂)₃— (wherein Ph is phenyl),

—CONH—(CH₂)₆—,

—CON(CH₃)—(CH₂)₆—,

—CON(Ph)-(CH₂)₆— (wherein Ph is phenyl),

—CONH—(CH₂)₂NH(CH₂)₃—,

—CONH—(CH₂)₆NH(CH₂)₃—,

—CH₂O—CONH—(CH₂)₃—,

—CH₂O—CONH—(CH₂)₆—,

—S—(CH₂)₃—,

—(CH₂)₂S(CH₂)₃—,

—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,

—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,

—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,

—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,

—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,

—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—

—C(O)O—(CH₂)₃—,

—C(O)O—(CH₂)₆—,

—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,

—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,

—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃—,

—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,

and the like.

Other examples of the X¹ include, for example the following groups:

wherein R⁴¹ is each independently a hydrogen atom, a phenyl group, analkyl group having 1-6 carbon atoms, or a C₁₋₆ alkoxy group, preferablya methyl group;

D is a group selected from

—CH₂O(CH₂)₂—,

—CH₂O(CH₂)₃—,

—CF₂O(CH₂)₃—,

—(CH₂)₂—,

—(CH₂)₃—,

—(CH₂)₄—,

—CONH—(CH₂)₃—,

—CON(CH₃)—(CH₂)₃—,

—CON(Ph)-(CH₂)₃— (wherein Ph is a phenyl group), and

wherein R⁴² is each independently a hydrogen atom, a C₁₋₆ alkyl group ora C₁₋₆ alkoxy group, preferably a methyl group or a methoxy group, morepreferably a methyl group,

E is —(CH₂)_(n)— wherein n is an integer of 2-6,

D binds to PFPE of the main backbone, and E binds to a group opposite toPFPE.

Further other examples of the X¹ group include the following groups:

wherein R⁴¹ is each independently a hydrogen atom, a phenyl group, analkyl group having 1-6 carbon atoms, or a C₁₋₆ alkoxy group, preferablya methyl group;

in each X¹ group, any one of T is a following group which binds to PFPEof the main backbone:

—CH₂O(CH₂)₂—,

—CH₂O(CH₂)₃—,

—CF₂O(CH₂)₃—,

—(CH₂)₂—,

—(CH₂)₃—,

—(CH₂)₄—,

—CONH—(CH₂)₃—,

—CON(CH₃)—(CH₂)₃—,

—CON(Ph)-(CH₂)₃— wherein Ph is phenyl, or

wherein R⁴² is each independently a hydrogen atom, a C₁₋₆ alkyl group ora C₁₋₆ alkoxy group, preferably a methyl group or a methoxy group, morepreferably a methyl group,

at least one of the other T is —(CH₂)_(n″)— (wherein n″ is an integer of2-6) attached to the group opposite to PFPE, and

the others are each independently a methyl group or a phenyl group, ifany.

In other embodiment, X¹ is a group of the formula:—(R¹⁶)_(x)—(CFR¹⁷)_(y)—(CH₂)_(z)—. In the formula, x, y and z are eachindependently an integer of 0-10, the sum of x, y and z is 1, and theoccurrence order of the respective repeating units in parentheses is notlimited in the formula.

In the formula, R¹⁶ is each independently at each occurrence an oxygenatom, phenylene, carbazolylene, —NR²⁰— wherein R²⁰ is a hydrogen atom oran organic group) or a divalent organic group. Preferably, R¹⁶ is anoxygen atom or a divalent polar group.

Examples of the “divalent polar group” in Q include, but are notparticularly limited to, —C(O)—, —C(═NR²¹)—, and —C(O)NR²¹— wherein R²¹is a hydrogen atom or a lower alkyl group. The “lower alkyl group” is,for example, an alkyl group having 1-6 carbon atoms, for example,methyl, ethyl, n-propyl, which may be substituted by one or morefluorine atoms.

In the formula, R¹⁷ is each independently at each occurrence a hydrogenatom, a fluorine atom or a lower fluoroalkyl group, preferably afluorine atom. The “lower fluoroalkyl group” is, for example, preferablya fluoroalkyl group having 1-6 carbon atoms, preferably 1-3 carbonatoms, preferably a perfluoroalkyl group having 1-3 carbon atoms, morepreferably a trifluoromethyl group, and a pentafluoroethyl group,further preferably a trifluoromethyl group.

In this embodiment, X¹ is preferably is a group of the formula:—(O)_(x)—(CF₂)_(y)—(CH₂)_(z)— wherein x, y and z are as defined above,and the occurrence order of the respective repeating units inparentheses is not limited in the formula.

Examples of the group of the formula: —(O)_(x)—(CF₂)_(y)—(CH₂)_(z)—include, for example, —(O)_(x′)—(CH₂)_(z″)—O—[(CH₂)_(z′″)—O-]_(z″″), and—(O)_(x′)—(CF₂)_(y″)—(CH₂)_(z″)—O—[(CH₂)_(z′″)—O-]_(z″″) wherein x′ is 0or 1, y″, z″ and z′″ are each independently an integer of 1-10, and z″″is 0 or 1. It is noted that these groups are attached to PFPE at itsleft side terminal.

In another embodiment, X¹ is —O—CFR¹³—(CF₂)_(e)—.

R¹³ is each independently a fluorine atom or a lower fluoroalkyl group.The lower fluoroalkyl group is, for example, a fluoroalkyl group having1-3 carbon atoms, preferably a perfluoroalkyl group having 1-3 carbonatoms, more preferably a trifluoromethyl group, and a pentafluoroethylgroup, further preferably a trifluoromethyl group.

“e” is each independently 0 or 1.

In one embodiment, R¹³ is a fluorine atom, and e is 1.

In the formula, t is each independently an integer of 1-10, preferablyan integer of 1-6.

In the formula, X² is each independently at each occurrence a singlebond or a divalent organic group. X² is preferably an alkylene grouphaving 1-20 carbon atoms, more preferably, —(CH₂)_(u)— wherein u is aninteger of 0-2.

The compound of the formulae (A1) and (A2) can be obtained, for example,by introducing an iodine into a terminal of a perfluoropolyetherderivative corresponding to the Rf-PFPE-moiety as a raw material, andreacting it with a vinyl monomer corresponding to —CH₂CR¹²(X²YA)-.

Alternatively, the compound can be produced by synthesizing a compoundhaving a precursor group corresponding to the Y-A moiety, and convertingthe precursor to the Y-A moiety by using a method known in the art.

The method for converting is not particularly limited. For example, aknown reaction for forming a carbon-carbon unsaturated bond, for examplean elimination reaction such as dehydration reaction ordehydrohalogenation reaction, or a known method for adding a compoundhaving a carbon-carbon unsaturated bond to a terminal of the molecularcorresponding to the Y-A moiety or substituting the terminal by thecompound having a carbon-carbon unsaturated bond can be used. Thoseskilled in the art can select a suitable reaction and its reactioncondition depending on a structure of the compound.Formula (B1) and (B2):(Rf-PFPE)_(β′)—X³—(Y-A)_(β)  (B1)(A-Y)_(β)—X³-PFPE-X³—(Y-A)_(β)  (B2)

In the formulae (B1) and (B2), Rf, PFPE, Y and A are as defined for theformulae (A1) and (A2).

In the formula, X³ is each independently a single bond or a 2-10 valentorganic group. The X³ group is recognized to be a linker which connectsbetween a perfluoropolyether moiety (an Rf-PFPE moiety or -PFPE-moiety)providing mainly water-repellency, surface slip property and the likeand a group having a carbon-carbon unsaturated bond (specifically, the Agroup or a group containing the A group) providing an ability to bind toa base material in the compound of the formula (B1) and (B2). Therefore,the X³ group may be any organic group as long as the compound of theformula (B1) and (B2) can stably exist.

In the formula, β is an integer of 1-9, and β′ is an integer of 1-9. βand β′ are determined depending on the valence number of the X³ group.In the formula (B1), the sum of β and β′ is the valence number of the X³group. For example, when X³ is a 10 valent organic group, the sum of βand β′ is 10, for example, β is 9 and β′ is 1, β is 5 and β′ is 5, or βis 1 and β′ is 9. When X³ is a divalent organic group, β and β′ are 1.In the formula (B2), β is a value obtained by subtracting 1 from thevalence number of the X³ group.

X³ is preferably a 2-7 valent, more preferably 2-4 valent, morepreferably a divalent organic group.

Examples of X³ include, but are not particularly limited to, the samegroups as that for X¹.

The compound of the formulae (B1) and (B2) can be obtained, for example,by introducing a hydroxyl group into a terminal of a perfluoropolyetherderivative corresponding to the Rf-PFPE-moiety as a raw material, andsubjecting it to Williamson reaction with a compound having a groupcorresponding to the —Y-A moiety, for example, a compound having ahalogenated alkyl group at the terminal.

Alternatively, the compound can be produced by synthesizing a compoundhaving a precursor group corresponding to the Y-A moiety, and convertingthe precursor to the Y-A moiety by using a method known in the art.

The method for converting is not particularly limited. For example, aknown reaction for forming a carbon-carbon unsaturated bond, for examplean elimination reaction such as dehydration reaction ordehydrohalogenation reaction, or a known method for adding a compoundhaving a carbon-carbon unsaturated bond to a terminal of the molecularcorresponding the Y-A moiety or substituting the terminal by thecompound having a carbon-carbon unsaturated bond can be used. Thoseskilled in the art can select a suitable reaction and its reactioncondition depending on a structure of the compound.Formulae (C1) and (C2):(Rf-PFPE)_(γ′)—X⁴—(SiR^(a) _(k)R^(b) _(l)R^(c) _(m)R^(d) _(n))_(γ)  (C1)(SiR^(a) _(k)R^(b) _(l)R^(c) _(m)R^(d) _(n))_(γ)—X⁴-PFPE-X⁴—(SiR^(a)_(k)R^(b) _(l)R^(c) _(m)R^(d) _(n))_(γ)  (C2)

In the formulae (C1) and (C2), Rf and PFPE are defined as that for theformulae (A1) and (A2).

In the formula, X⁴ is each independently a single bond or a 2-10 valentorganic group. The X⁴ group is recognized to be a linker which connectsbetween a perfluoropolyether moiety (an Rf-PFPE moiety or -PFPE-moiety)providing mainly water-repellency, surface slip property and the likeand a group having a carbon-carbon unsaturated bond (specifically, the Agroup or a group containing the A group (—SiR^(a) _(k)R^(b) _(l)R^(c)_(m)R^(d) _(n) group)) providing an ability to bind to a base materialin the compound of the formula (C1) and (C2). Therefore, the X⁴ groupmay be any organic group as long as the compound of the formula (C1) and(C2) can stably exist.

In the formula, γ is an integer of 1-9, and γ′ is an integer of 1-9. γand γ′ are determined depending on the valence number of the X⁴ group.In the formula (C1), the sum of γ and γ′ is the valence number of the X⁴group. For example, when X⁴ is a 10 valent organic group, the sum of γand γ′ is 10, for example, γ is 9 and γ′ is 1, γ is 5 and γ′ is 5, or γis 1 and γ′ is 9. When X⁴ is a divalent organic group, γ and γ′ are 1.In the formula (C2), γ is a value obtained by subtracting 1 from thevalence number of the X⁴ group.

X⁴ is preferably a 2-7 valent, more preferably 2-4 valent, morepreferably a divalent organic group.

Examples of X⁴ include, but are not particularly limited to, the samegroup as that for X¹.

In the formula, R^(a) is each independently at each occurrence —Z—SiR⁷¹_(p)R⁷² _(q)R⁷³ _(r)R⁷⁴ _(s).

In the formula, Z is each independently at each occurrence an oxygenatom or a divalent organic group.

Preferably, Z is a divalent organic group. Z does not include a groupwhich forms a siloxane bond together with a Si atom (Si atom to whichR^(a) attaches) present in the end of the molecular backbone of theformula (C1) or the formula (C2).

Z is preferably, a C₁₋₆ alkylene group, —(CH₂)_(g)—O—(CH₂)_(h)— whereing is an integer of 0-6, for example, an integer of 1-6, h is an integerof 0-6, for example, an integer of 1-6, or -phenylene-(CH₂)_(i)— whereini is an integer of 0-6, more preferably a C₁₋₃ alkylene group. Thesegroups may be substituted by one or more substituents selected from, forexample, a fluorine atom, a C₁₋₆ alkyl group, a C₂₋₆ alkenyl group, anda C₂₋₆ alkynyl group.

In the formula, R⁷¹ is each independently at each occurrence R^(a′).R^(a′) has the same definition as that of R^(a),

In R^(a), the number of Si atoms which are linearly connected via the Zgroup is up to five. That is, in R^(a), when there is at least one R⁷¹,there are two or more Si atoms which are linearly connected via the Zgroup in R^(a). The number of such Si atoms which are linearly connectedvia the Z group is up to five. It is noted that “the number of such Siatoms which are linearly connected via the Z group in R^(a)” is equal tothe repeating number of —Z—Si— which are linearly connected in R^(a).

For example, one example in which Si atoms are connected via the Z groupin R^(a) is shown below.

In the above formula, * represents a position binding to Si of the mainbackbone, and . . . represents that a predetermined group other than ZSibinds thereto, that is, when all three bonds of a Si atom are . . . , itmeans an end point of the repeat of ZSi. The number on the rightshoulder of Si means the number of occurrences of Si which is linearlyconnected via the Z group from *. In other words, in the chain in whichthe repeat of ZSi is completed at Si², “the number of such Si atomswhich are linearly connected via the Z group in R^(a)” is 2. Similarly,in the chain in which the repeat of ZSi is completed at Si³, Si⁴ andSi⁵, respectively, “the number of such Si atoms which are linearlyconnected via the Z group in R^(a)” is 3, 4 and 5. It is noted that asseen from the above formula, there are some ZSi chains, but they neednot have the same length and may be have arbitrary length.

In a preferred embodiment, as shown below, “the number of such Si atomswhich are linearly connected via the Z group in R^(a)” is 1 (leftformula) or 2 (right formula) in all chains.

In one embodiment, the number of such Si atoms which are linearlyconnected via the Z group in R^(a) is 1 or 2, preferably 1.

In the formula, R⁷² is each independently at each occurrence —X⁵—Y-A. Yand A are as defined above.

X⁵ is each independently at each occurrence a single bond or a divalentorganic group. X⁵ is preferably a single bond, a C₁₋₆ alkylene group,—(CH₂)_(g)—O—(CH₂)_(h)— (wherein g is an integer of 1-6, h is an integerof 1-6) or, -phenylene-(CH₂)_(i)— (wherein i is an integer of 0-6), morepreferably a single bond or a C₁₋₃ alkylene group. These groups may besubstituted by one or more substituents selected from, for example, afluorine atom, a C₁₋₆ alkyl group, a C₂₋₆ alkenyl group, and a C₂₋₆alkynyl group.

R⁷² is preferably —CH₂—CH═CH₂.

In the formula, R⁷³ is each independently at each occurrence a hydroxylgroup or a hydrolyzable group.

The “hydrolyzable group” as used herein represents a group which is ableto undergo a hydrolysis reaction. Examples of the hydrolyzable groupinclude —OR, —OCOR, —O—N═C(R)₂, —N(R)₂, —NHR, halogen (wherein R is asubstituted or non-substituted alkyl group having 1-4 carbon atoms),preferably —OR (an alkoxy group). Examples of R include anon-substituted alkyl group such as a methyl group, an ethyl group, apropyl group, an isopropyl group, a n-butyl group, an isobutyl group; asubstituted alkyl group such as a chloromethyl group. Among them, analkyl group, in particular a non-substituted alkyl group is preferable,a methyl group or an ethyl group is more preferable. The hydroxyl groupmay be, but is not particularly limited to, a group generated byhydrolysis of a hydrolyzable group.

Preferably, R⁷³ is —OR wherein R is a substituted or non-substitutedC₁₋₃ alkyl group, more preferably a methyl group.

In the formula, R⁷⁴ is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms, more preferably a methyl group.

In the formula, p is each independently at each occurrence an integer of0-3; q is each independently at each occurrence, an integer of 0-3; r iseach independently at each occurrence an integer of 0-3; s is eachindependently at each occurrence an integer of 0-3. However, p+q+r+s(the sum of p, q, r and s) is 3.

In a preferably embodiment, in the terminal R^(a′) in R^(a) (when R^(a′)is absent, R^(a)), q is preferably 2 or more, for example 2 or 3, morepreferably 3.

In the formula, R^(b) is each independently at each occurrence —X⁵—Y-A.X⁵, Y and A are as defined above. R^(b) is preferably —CH₂—CH═CH₂.

In the formula, R^(c) is each independently at each occurrence ahydroxyl group or a hydrolyzable group.

R^(c) is preferably a hydroxyl group, —OR, —OCOR, —O—N═C(R)₂, —N(R)₂,—NHR, halogen (wherein R is a substituted or non-substituted alkyl grouphaving 1-4 carbon atoms), preferably —OR. R is a non-substituted alkylgroup such as a methyl group, an ethyl group, a propyl group, anisopropyl group, a n-butyl group, an isobutyl group; a substituted alkylgroup such as a chloromethyl group. Among them, an alkyl group, inparticular a non-substituted alkyl group is preferable, a methyl groupor an ethyl group is more preferable. The hydroxyl group may be, but isnot particularly limited to, a group generated by hydrolysis of ahydrolyzable group. R^(c) is more preferably —OR wherein R is asubstituted or non-substituted C₁₋₃alkyl group, more preferably methylgroup.

In the formula, R^(d) is each independently at each occurrence ahydrogen atom or a lower alkyl group. The lower alkyl group ispreferably an alkyl group having 1-20 carbon atoms, more preferably analkyl group having 1-6 carbon atoms, further preferably methyl group.

In the formulae, k is each independently at each occurrence an integerof 0-3; 1 is each independently at each occurrence an integer of 0-3; mis each independently at each occurrence, an integer of 0-3; n is eachindependently at each occurrence an integer of 0-3. However, k+l+m+n(the sum of k, l, m and n) is 3.

In the formulae (C1) and (C2), in —(SiR^(a) _(k)R^(b) _(l)R^(c)_(m)R^(d) _(n))_(r), at least one Y-A group is present.

The compound of the formulae (C1) and (C2) can be obtained, for example,by introducing a —SiHal₃ group (Hal is a halogen) into aperfluoropolyether derivative corresponding to the Rf-PFPE-moiety byhydrosilylation, etc., and subjecting it to a reaction with a Grignardreagent corresponding to the —Y-A moiety, for example,Hal-Mg—CH₂—CH═CH₂, etc.

Alternatively, the compound can be produced by synthesizing a compoundhaving a precursor group corresponding to the Y-A moiety, and convertingthe precursor to the Y-A moiety by using a method known in the art.

The method for converting is not particularly limited. For example, aknown reaction for forming a carbon-carbon unsaturated bond, for examplean elimination reaction such as dehydration reaction ordehydrohalogenation reaction, or a known method for adding a compoundhaving a carbon-carbon unsaturated bond to a terminal of the molecularcorresponding the Y-A moiety or substituting the terminal by thecompound having a carbon-carbon unsaturated bond can be used. Thoseskilled in the art can select a suitable reaction and its reactioncondition depending on a structure of the compound.Formulae (D1) and (D2):(R⁹¹—Rf′)_(δ′)—X⁶—(Y-A)_(δ)  (D1)(A-Y)_(δ)—X⁶—Rf′—X⁶—(Y-A)_(δ)  (D2)

In the formulae (D1) and (D2), Y and A are defined as that for theformulae (A1) and (A2).

In the formula, X⁶ is each independently a single bond or a 2-10 valentorganic group. The X⁶ group is recognized to be a linker which connectsbetween a perfluoropolyether moiety (an R⁹¹—Rf′— or —Rf′—) providingmainly water-repellency, surface slip property and the like and a grouphaving a carbon-carbon unsaturated bond (specifically, the A group or agroup containing the A group) providing an ability to bind to a basematerial in the compound of the formula (D1) and (D2). Therefore, the X⁶group may be any organic group as long as the compound of the formula(D1) and (D2) can stably exist.

In the formula, δ is an integer of 1-9, and is determined depending onthe valence number of X⁶. For example, when X⁶ is a 10 valent organicgroup, δ is 9, and when X⁶ is a divalent organic group, δ is 1.

In the formula, δ is an integer of 1-9, and δ′ is an integer of 1-9. δand δ′ are determined depending on the valence number of the X⁶ group.In the formula (D1), the sum of δ and δ′ is the valence number of the X⁶group. For example, when X⁶ is a 10 valent organic group, the sum of δand δ′ is 10, for example, δ is 9 and δ′ is 1, δ is 5 and δ′ is 5, or δis 1 and δ′ is 9. When X⁶ is a divalent organic group, δ and δ′ are 1.In the formula (D2), δ is a value obtained by subtracting 1 from thevalence number of the X⁶ group.

X⁶ is preferably a 2-7 valent, more preferably 2-4 valent, morepreferably a divalent organic group.

Examples of X⁶ include, but are not particularly limited to, the samegroup as that for X¹.

In the formula, R⁹¹ is a fluorine atom, —CHF₂ or —CF₃, preferably afluorine atom or —CF₃.

Rf′ is a perfluoroalkylene group having 1-20 carbon atoms. Rf′ haspreferably 1-12 carbon atoms, more preferably 1-6 carbon atoms, furtherpreferably 3-6 carbon atoms. Examples of the specific Rf′ include —CF₂—,—CF₂CF₂—, —CF₂CF₂CF₂—, —CF(CF₃)—, —CF₂CF₂CF₂CF₂—, —CF₂CF(CF₃)—,—C(CF₃)—, —(CF₂)₄CF₂—, —(CF₂)₂CF(CF₃)—, —CF₂C(CF₃)—, —CF(CF₃)CF₂CF₂CF₂—,—(CF₂)₅CF₂—, —(CF₂)₃CF(CF₃)₂, —(CF₂)₄CF(CF₃)₂, —C₈F₁₇. Among them, astraight perfluoroalkylene having 3-6 carbon atoms, for example,—CF₂CF₂CF₂CF₂—, —CF₂CF₂CF₂—, etc.

The compound of the formulae (D1) and (D2) can be obtained, for example,by introducing iodine into a terminal of a perfluoropolyether derivativecorresponding to the Rf-PFPE-moiety as a raw material, and subjecting itto a dehydrohalogenation reaction, etc.

Alternatively, the compound can be produced by synthesizing a compoundhaving a precursor group corresponding to the Y-A moiety, and convertingthe precursor to the Y-A moiety by using a method known in the art.

The method for converting is not particularly limited. For example, aknown reaction for forming a carbon-carbon unsaturated bond, for examplean elimination reaction such as dehydration reaction ordehydrohalogenation reaction, or a known method for adding a compoundhaving a carbon-carbon unsaturated bond to a terminal of the molecularcorresponding the Y-A moiety or substituting the terminal by thecompound having a carbon-carbon unsaturated bond can be used. Thoseskilled in the art can select a suitable reaction and its reactioncondition depending on a structure of the compound.

The surface-treating agent of the present invention may be diluted witha solvent, Examples of the solvent include, but are not particularlylimited to, for example, a solvent selected from the group consisting ofperfluorohexane, CF₃CF₂CHCl₂, CF₃CH₂CF₂CH₃, CF₃CHFCHFC₂F₅,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane,1,1,2,2,3,3,4-heptafluorocyclopentane (ZEORORA H (trade name), etc.),C₄F₉OCH₃, C₄F₉OC₂H₅, CF₃CH₂OCF₂CHF₂, C₆F₁₃CH═CH₂, xylene hexafluoride,perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol,pentafluoropropanol, hexafluoroisopropanol, HCF₂CF₂CH₂OH, methyltrifluoromethanesulfonate, trifluoroacetic acid andCF₃O(CF₂CF₂O)_(m)(CF₂O)_(n)CF₂CF₃ [wherein m and n are eachindependently an integer of 0 or more and 1000 or less, the occurrenceorder of the respective repeating units in parentheses with thesubscript m or n is not limited in the formula, with the proviso thatthe sum of m and n is 1 or more.],1,1-dichloro-2,3,3,3-tetrafluoro-1-propene,1,2-dichloro-1,3,3,3-tetrafluoro-1-propene,1,2-dichloro-3,3,3-trichloro-1-propene,1,1-dichloro-3,3,3-trichloro-1-propene,1,1,2-trichloro-3,3,3-trichloro-1-propene,1,1,1,4,4,4-hexafluoro-2-butene. These solvents may be used alone or asa mixture of 2 or more compound.

The above-mentioned surface-treating agent may comprise other componentsin addition to a fluorine-containing compound having a carbon-carbonunsaturated bond at the molecular terminal. Examples of the othercomponents include, but are not particularly limited to, for example, a(non-reactive) fluoropolyether compound which may be also understood asa fluorine-containing oil, preferably a perfluoro(poly)ether compound(hereinafter, referred to as “the fluorine-containing oil”), a(non-reactive) silicone compound which may be also understood as asilicone oil (hereinafter referred to as “a silicone oil”), a catalyst,and the like.

Examples of the above-mentioned fluorine-containing oil include, but arenot particularly limited to, for example, a compound of the followinggeneral formula (3) (a perfluoro(poly)ether compound).Rf¹—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—Rf²  (3)

In the formula, Rf¹ represents a C₁₋₁₆ alkyl group which may besubstituted by one or more fluorine atoms (preferably, a C₁₋₁₆perfluoroalkyl group), Rf² represents a C₁₋₁₆ alkyl group which may besubstituted by one or more fluorine atoms (preferably, a C₁₋₁₆perfluoroalkyl group), a fluorine atom or a hydrogen atom, and morepreferably, Rf¹ and Rf² is each independently a C₁₋₃ perfluoroalkylgroup.

Subscripts a′, b′, c′ and d′ represent the repeating number of each offour repeating units of perfluoropolyether which constitute a mainbackbone of the polymer, and are each independently an integer of 0 ormore and 300 or less, and the sum of a′, b′, c′ and d′ is at least 1,preferably 1-300, more preferably 20-300. The occurrence order of therespective repeating units in parentheses with the subscript a′, b′, c′or d′ is not limited in the formulae. Among these repeating units, the—(OC₄F₈)— group may be any of —(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂CF₂)—,—(OCF₂CF(CF₃)CF₂)—, —(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—,—(OCF₂C(CF₃)₂)—, —(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F₅)CF₂)— and—(OCF₂CF(C₂F₅))—, preferably —(OCF₂CF₂CF₂CF₂). The —(OC₃F₆)— group maybe any of —(OCF₂CF₂CF₂)—, —(OCF(CF₃)CF₂)— and —(OCF₂CF(CF₃))—,preferably —(OCF₂CF₂CF₂)—. The —(OC₂F₄)— group may be any of —(OCF₂CF₂)—and —(OCF(CF₃))—, preferably —(OCF₂CF₂)—.

Examples of the perfluoropolyether compound of the above general formula(3) include a compound of any of the following general formulae (3a) and(3b) (may be one compound or a mixture of two or more compounds).Rf¹—(OCF₂CF₂CF₂)_(b″)—Rf²  (3a)Rf¹—(OCF₂CF₂CF₂CF₂)_(a″)—(OCF₂CF₂CF₂)_(b″)—(OCF₂CF₂)_(c″)—(OCF₂)_(d″)—Rf²  (3b)In these formulae:

Rf¹ and Rf² are as defined above; in the formula (3a), b″ is an integerof 1 or more and 100 or less; and in the formula (3b), a″ and b″ areeach independently an integer of 1 or more and 30 or less, and c″ and d″are each independently an integer of 1 or more and 300 or less. Theoccurrence order of the respective repeating units in parentheses withthe subscript a″, b″, c″ or d″ is not limited in the formulae.

The above-mentioned fluorine-containing oil may have an averagemolecular weight of 1,000-30,000. By having such average molecularweight, high surface slip property can be obtained.

The fluorine-containing oil may be contained in the surface-treatingagent of the present invention, for example, at 0-500 parts by mass,preferably 0-400 parts by mass, more preferably 5-300 parts by mass withrespect to 100 parts by mass of the fluorine-containing compound havinga carbon-carbon unsaturated bond at the molecular terminal (as the totalmass when two or more compounds are used; hereinafter the same shallapply).

The compound of the general formula (3a) and the compound of the generalformula (3b) may be used alone or in combination. The compound of thegeneral formula (3b) is preferable than the compound of the generalformula (3a) since the compound of the general formula (3b) provideshigher surface slip property than the compound of the general formula(3a). When they are used in combination, the ratio by mass of thecompound of the general formula (3a) to the compound of the generalformula (3b) is preferably 1:1 to 1:30, more preferably 1:1 to 1:10. Byapplying such ratio by mass, a perfluoropolyether group-containingsilane-based coating which provides a good balance of surface slipproperty and friction durability can be obtained.

In one embodiment, the fluorine-containing oil comprises one or morecompounds of the general formula (3b). In such embodiment, the massratio of the fluorine-containing compound having a carbon-carbonunsaturated bond at the molecular terminal to the compound of theformula (3b) in the surface-treating agent is preferably 4:1 to 1:4.

In a preferable embodiment, when a surface-treating layer is formed byusing vacuum deposition, an average molecular weight of thefluorine-containing oil may be higher than an average molecular weightof the fluorine-containing compound having a carbon-carbon unsaturatedbond at the molecular terminal. By selecting such average molecularweights, more excellent surface slip property and friction durabilitycan be obtained.

From the other point of view, the fluorine-containing oil may be acompound of the general formula Rf³—F wherein Rf³ is a C₅₋₁₆perfluoroalkyl group. In addition, the fluorine-containing oil may be achlorotrifluoroethylene oligomer. The compound of Rf³—F or thechlorotrifluoroethylene oligomer is preferable because the compoundshave high affinity for the fluorine-containing compound having acarbon-carbon unsaturated bond at the molecular terminal wherein aterminal is a C₁₋₁₆ perfluoroalkyl group.

The fluorine-containing oil contributes to increasing of surface slipproperty of the surface-treating layer.

Examples of the above-mentioned silicone oil include, for example, aliner or cyclic silicone oil having 2,000 or less siloxane bonds. Theliner silicone oil may be so-called a straight silicone oil and amodified silicon oil. Examples of the straight silicone oil includedimethylsilicone oil, methylphenylsilicone oil, andmethylhydrogensilicone oil. Examples of the modified silicone oilinclude that which is obtained by modifying a straight silicone oil withalkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino,epoxy, carboxyl, alcohol, or the like. Examples of the cyclic siliconeoil include, for example, cyclic dimethylsiloxane oil.

The silicone oil may be contained in the surface-treating agent of thepresent invention, for example, at 0-300 parts by mass, preferably 0-200parts by mass with respect to 100 parts by mass of thefluorine-containing compound having a carbon-carbon unsaturated bond atthe molecular terminal (as the total mass when two or more compounds areused; hereinafter the same shall apply).

The silicone oil contributes to increasing of surface slip property ofthe surface-treating layer.

Examples of the above-mentioned catalyst include an acid (for example,acetic acid, trifluoroacetic acid, etc.), a base (for example, ammonia,triethylamine, diethylamine, etc.), a transition metal (for example, Ti,Ni, Sn, etc.), and the like.

When the fluorine-containing compound having a carbon-carbon unsaturatedbond at the molecular terminal has a hydrolyzable group, the catalystfacilitates hydrolysis and dehydration-condensation of the compound tofacilitate a formation of the surface-treating layer.

The surface-treating agent of the present invention is impregnated intoa porous material, for example, a porous ceramic material, a metal fiberfor example that obtained by solidifying a steel wool to obtain apellet. The pellet can be used, for example, in vacuum deposition.

By forming the surface-treating layer on a surface of the base materialby using the surface-treating agent of the present invention, thesurface-treating layer having high alkali resistance and havingwater-repellency, oil-repellency, antifouling property (for example,preventing from adhering a fouling such as fingerprints), waterproofproperty (preventing the ingress of water into an electrical member, andthe like), surface slip property (or lubricity, for example, wipingproperty of a fouling such as fingerprints and excellent tactile feelingin a finger), ultraviolet resistance, and the like depending on acomposition of the surface-treating agent used can be obtained.

The base material usable in the present invention may be composed of anysuitable material such as an inorganic material (for example, a glass,sapphire glass), a resin (may be a natural or synthetic resin such as acommon plastic material, specifically an acrylic resin, a polycarbonateresin, and may be in form of a plate, a film, or others), a metal (maybe a simple substance of a metal such as aluminum, copper, or iron, or acomplex such as alloy or the like), a ceramic, a semiconductor (silicon,germanium, or the like), a fiber (a fabric, a non-woven fabric, or thelike), a fur, a leather, a wood, a pottery, a stone, an architecturalmember or the like.

For example, when an article to be produced is an optical member, amaterial constituting the surface of the base material may be a materialfor an optical member, for example, a glass or a transparent plastic.For example, when an article to be produced is an optical member, anylayer (or film) such as a hard coating layer or an antireflection layermay be formed on the surface (for example, outermost layer) of the basematerial. As the antireflection layer, either a single antireflectionlayer or a multi antireflection layer may be used. Examples of aninorganic material usable in the antireflection layer include SiO₂, SiO,ZrO₂, TiO₂, TiO, Ti₂O₃, Ti₂O₅, Al₂O₃, Ta₂O₅, CeO₂, MgO, Y₂O₃, SnO₂,MgF₂, WO₃, and the like. These inorganic materials may be used alone orin combination with two or more (for example, as a mixture). When multiantireflection layer is formed, preferably, SiO₂ and/or SiO are used inthe outermost layer. When an article to be produced is an optical glasspart for a touch panel, it may have a transparent electrode, forexample, a thin layer comprising indium tin oxide (ITO), indium zincoxide, or the like on a part of the surface of the base material(glass). Furthermore, the base material may have an insulating layer, anadhesive layer, a protecting layer, a decorated frame layer (I-CON), anatomizing layer, a hard coating layer, a polarizing film, a phasedifference film, a liquid crystal display module, and the like,depending on its specific specification.

The preferable base material is a glass or a sapphire glass. As theglass, a soda-lime glass, an alkali aluminosilicate glass, aborosilicate glass, a non-alkaline glass, a crystal glass, a quartzglass is preferable, a chemically strengthened soda-lime glass, achemically strengthened alkali aluminosilicate glass, and a chemicallystrengthened borosilicate glass are more preferable.

The shape of the base material is not specifically limited. The regionof the surface of the base material on which the surface-treating layershould be formed may be at least a part of the surface of the basematerial, and may be appropriately determined depending on use, thespecific specification, and the like of the article to be produced.

In a preferable embodiment, the base material has a Si—H bond or a C—Hbond on its surface.

The Si—H bond or the C—H bond may be introduced by pretreatment thesurface of the base material0. For example, the Si—H bond or the C—Hbond can be introduced by plasma-treating the surface of the basematerial.

The Si—H bond or the C—H bond can be introduced by forming a layerhaving a Si—H bond or a C—H bond on the surface of the base material.For example, the layer having a Si—H bond or a C—H bond can be formed onthe surface of the base material by forming a layer of silicon dioxideon the surface of the base material and plasma-treating it, or forming adiamond-like carbon layer.

In one embodiment, the base material may have a hydroxyl group inaddition to the Si—H bond or the C—H bond on the surface. By using suchbase material, for example, when the surface-treating agent having a Siatom to which a hydrolyzable group attaches in addition to thecarbon-carbon unsaturated bond at the terminal is used, thesurface-treating layer can be bonded to the base material more strongly.

A method for forming the surface-treating layer on the surface of thebase material includes, for example, the following methods.

The formation of the surface-treating layer can be performed by applyingthe above surface-treating agent on the surface of the base materialsuch that the surface-treating agent coats the surface. The method ofcoating is not specifically limited. For example, a wet coating methodor a dry coating method can be used.

Examples of the wet coating method include dip coating, spin coating,flow coating, spray coating, roll coating, gravure coating, and asimilar method.

Examples of the dry coating method include deposition (usually, vacuumdeposition), sputtering, CVD and a similar method. The specific examplesof the deposition method (usually, vacuum deposition) include resistanceheating, electron beam, high-frequency heating using microwave, etc.,ion beam, and a similar method. The specific examples of the CVD methodinclude plasma-CVD, optical CVD, thermal CVD and a similar method. Thedeposition method is will be described below in more detail.

Additionally, coating can be performed by an atmospheric pressure plasmamethod.

When the wet coating method is used, the surface-treating agent of thepresent invention is diluted with a solvent, and then it is applied tothe surface of the base material. In view of stability of thesurface-treating agent of the present invention and volatile property ofthe solvent, the following solvents are preferably used: a C₅₋₁₂aliphatic perfluorohydrocarbon (for example, perfluorohexane,perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); anaromatic polyfluorohydrocarbon (for example,bis(trifluoromethyl)benzene); an aliphatic polyfluorohydrocarbon (forexample, C₆F₁₃CH₂CH₃ (for example, ASAHIKLIN (registered trademark)AC-6000 manufactured by Asahi Glass Co., Ltd.),1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEORORA (registeredtrademark) H manufactured by Nippon Zeon Co., Ltd.); hydrofluorocarbon(HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365mfc));hydrochlorofluorocarbon (for example, HCFC-225 (ASAHIKLIN (registeredtrademark) AK225)); a hydrofluoroether (HFE) (for example, an alkylperfluoroalkyl ether such as perfluoropropyl methyl ether (C₃F₇OCH₃)(for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Ltd.),perfluorobutyl methyl ether (C₄F₉OCH₃) (for example, Novec (trademark)7100 manufactured by Sumitomo 3M Ltd.), perfluorobutyl ethyl ether(C₄F₉OC₂H₅) (for example, Novec (trademark) 7200 manufactured bySumitomo 3M Ltd.), and perfluorohexyl methyl ether (C₂F₅CF(OCH₃)C₃F₇)(for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Ltd.)(the perfluoroalkyl group and the alkyl group may be liner orbranched)), or CF₃CH₂OCF₂CHF₂ (for example, ASAHIKLIN (registeredtrademark) AE-3000 manufactured by Asahi Glass Co., Ltd.),1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, VERTREL(registered trademark) Sion manufactured by Du Pont-MitsuiFluorochemicals Co., Ltd.) and the like. These solvents may be usedalone or as a mixture of 2 or more compound. Among them, thehydrofluoroether is preferable, perfluorobutyl methyl ether (C₄F₉OCH₃)and/or perfluorobutyl ethyl ether (C₄F₉OC₂H₅) are particularlypreferable. Furthermore, the solvent can be mixed with another solvent,for example, to adjust solubility of the fluorine-containing compoundhaving a carbon-carbon unsaturated bond at the molecular terminal.

When the dry coating method is used, the surface-treating agent of thepresent invention may be directly subjected to the dry coating method,or may be diluted with a solvent, and then subjected to the dry coatingmethod.

In one embodiment, the formation of the film is preferably performed sothat the surface-treating agent of the present invention is presenttogether with a catalyst for a reaction with the base material, forexample, a reaction with the Si—H bond or the C—H bond of the basematerial. Simply, when the wet coating method is used, after thesurface-treating agent of the present invention is diluted with asolvent, and just prior to applying it to the surface of the basematerial, the catalyst may be added to the diluted solution of thesurface-treating agent of the present invention. When the dry coatingmethod is used, the surface-treating agent of the present invention towhich a catalyst has been added is used itself in deposition (usually,vacuum deposition), or pellets may be used in the deposition (usually,the vacuum deposition), wherein the pellets is obtained by impregnatinga porous metal with the surface-treating agent of the present inventionto which the catalyst has been added. Alternatively, before thesurface-treating agent is provided on the surface of the base material,the catalyst may be present on the surface of the base material.

The catalyst is not particularly limited. For example, a metal catalyst,in particular platinum, palladium, rhodium, or ruthenium can be used,platinum is particularly preferred.

The film is post-treated as necessary. By performing the post-treatment,the bond between the surface-treating layer and the base material can bemore strength and the durability is increased. The post-treatment is notparticularly limited, and may be a thermal treatment. A temperature ofthe post-treatment is not particularly limited, and is 60° C. or more,preferably 100° C. or more, and a temperature at which thefluorine-containing compound having a carbon-carbon unsaturated bond atthe molecular terminal is not decomposed or less, for example, 250° C.or less, preferably 180° C. or less. The post-treatment is performedpreferably under an inert atmosphere, more preferably under vacuum.

In a preferable embodiment, before the surface of the base material istreated with the surface-treating agent, a concave portion may be formedon the surface of the base material. By forming the concave portion onthe surface of the base material, when the surface of the base materialis treated with the surface-treating agent, the surface-treating agentis filled in the concave portion. The surface-treating agent filled inthe concave portion can sustain the function of the surface-treatingagent for more long term because when the surface-treating layer iswasted by abrasion during the use, the surface-treating agent filled inthe concave portion function so as to supplement the surface-treatingagent wasted.

A shape, size and quantity of the concave portion are not particularlylimited. It is preferable that the surface state of the base materialafter the concave portion is formed and before the surface-treatingagent is applied is a state where Rmax (maximum height) of the surfaceof the base material is about 10-50 times, preferably 20-40 times Ra(center line average roughness). It is noted that Ra and Rmax aredefined in JIS B0601:1982.

Furthermore, when transparency of the base material is required, Ra ispreferably 60 nm or less, more preferably 40 nm or less. By setting Rato about 1/10 or less of the wavelength of visible light, thetransparency of the base material can be ensured.

A method of forming concave portion on the surface of the base materialis not particularly limited, and either chemical or physical method maybe used, in particular, etching, sputtering or the like can be used.

In a preferable embodiment, the surface-treating layer is formed byperforming a pretreatment of the base material so as to form a bindingsite with a compound in the surface-treating agent used on the surfaceof the base material; and applying the surface-treating agent of thepresent invention to the base material subjected to the pretreatment toform the surface-treating layer on the surface of the base material.

Therefore, the present invention provides a method for forming asurface-treating layer on a surface of a base material comprising thesteps of:

performing a pretreatment of the base material so as to form a bindingsite with a carbon-carbon unsaturated bond on the surface of the basematerial; and

applying the surface-treating agent of the present invention to the basematerial subjected to the pretreatment to form the surface-treatinglayer on the surface of the base material.

Additionally, the present invention provides an apparatus for performingthe method described above, that is, a surface-treating layer formingapparatus for forming a surface-treating layer on a surface of the basematerial comprising:

a pretreatment unit for performing a pretreatment of the base materialto form a binding site with a fluorine-containing compound having acarbon-carbon unsaturated bond at its molecular terminal on the surfaceof the base material, and

a surface-treating layer forming unit for applying the surface-treatingagent of the present invention to the base material subjected to thepretreatment to form the surface-treating layer on the surface of thebase material.

Hereinafter, the method for forming a surface-treating layer and theapparatus for forming the surface-treating layer of the presentinvention will be described with reference to the drawings.

FIG. 1 is a block diagram showing one embodiment of a surface-treatinglayer forming apparatus for forming the surface-treating layer on a basematerial. FIG. 2 is a cross-sectional view schematically showing oneembodiment of the pretreatment unit 200.

As shown in FIG. 1, the surface-treating layer forming apparatus 100comprises a pretreatment unit 200 for performing the pretreatment of thebase material, a surface-treating layer forming unit 300 for forming thesurface-treating layer on the base material after the pretreatment, abase material transporting unit 400 for transport the base material tothe pretreatment unit 200 and the surface-treating layer forming unit300, a base material importing and exporting unit 500 for importing andexporting the base material, and a control unit 600 for controlling eachcomponent of the surface-treating layer forming apparatus 100. Thesurface-treating layer forming apparatus 100 is structured as amulti-chamber type apparatus. The base material transporting unit 400comprises a transporting chamber which is maintained in vacuum, and abase material transporting mechanism provided in the transportingchamber. The base material importing and exporting unit 500 comprises abase material holding part and a load-lock chamber, and transports thebase material in the base material holding part into the load-lockchamber, and import and export the base material via the load-lockchamber.

The pretreatment unit 200 performs the pretreatment to form a bindingsite with a fluorine-containing compound having a carbon-carbonunsaturated bond at its molecular terminal on the surface of the basematerial. In a preferable embodiment, the pretreatment unit 200 performsa surface treatment of the base material to bring a surface state of thebase material on which the surface-treating layer will be formed to astate where a surface-treating layer having high density can be formedby the surface-treating agent to be used, and is structured as a plasmatreating equipment for controlling amounts of O and H on the surface ofthe base material 220 in the embodiment.

The pretreatment unit 200 comprises a chamber 201, a base materialholder 202 for holding the base material 220 in the chamber 201, aplasma generating unit 203 for generating a plasma and providing theplasma in the chamber 201, and an exhaust mechanism 204 for evacuatingthe chamber 201.

An importing and exporting port 211 which communicates with thetransporting chamber and imports and exports the base material 220 isprovided on a side wall of the chamber 201. The importing and exportingport 211 can be opened and closed by a gate valve 212.

The plasma generating unit 203 is supplied with a treatment gascontaining a hydrogen gas, and generates the plasma containing hydrogenby a suitable method such as a microwave plasma, a inductively coupledplasma, a capacitively coupled plasma, or the like and supplies it inthe chamber 201.

The exhaust mechanism 204 comprises an exhaust pipe 213 connected tolower portion the chamber 201, a pressure adjustment valve 214 providedin the exhaust pipe 213, and a vacuum pump 215 for exhausting thechamber 201 via the exhaust pipe 213.

In the embodiment, the surface of the base material 220 is treated withthe plasma by holding the base material 220 on the base material holder202, maintaining a predetermined vacuum pressure in the chamber 201, andsupplying the plasma containing hydrogen to the chamber 201 from theplasma generating unit 203 under such state. Examples of the plasmacontaining hydrogen include, for example, a plasma containing a hydrogengas and a rare gas (for example, helium, neon, argon, krypton or xenon)or a hydrogen alone plasma.

Next, SAM is formed on the surface of the base material 220 as thesurface-treating layer by transferring the base material surface-treatedin the pretreatment unit 200 to an organic molecule film forming unit300, and supplying a SAM material gas to a vicinity of the base material220.

The control unit 600 comprises a controller provided with amicroprocessor (a computer) controlling each component of the apparatus100. The controller can control, for example, an output, a gas flowrate, and a vacuum level in the pretreatment unit 200, and a flow rateof a carrier gas, a vacuum level of the surface-treating layer formingunit 300. The controller is connected to a user interface including akeyboard that an operator inputs commands for managing the apparatus 100and a display for displaying visualized images of the operational statesof the apparatus 100. The controller is connected to a storage unit thatstores control programs for realizing various processes in the surfacetreatment performed in the apparatus 100 under the control of thecontroller, process recipes for respective components of the apparatus100 to perform the processes based on the processing conditions, andvarious databases. The process recipe is stored in a suitable storagemedium in the storage unit. If necessary, by reading the arbitraryprocess recipe from the storage unit and executing the process on thecontroller, the desired process is performed in the apparatus 100 underthe control of the controller.

The base material used in the method for forming the surface-treatinglayer and the apparatus for forming the surface-treating layer is notparticularly limited, but is preferably a base material having a networkstructure of Si and O at least on its surface. Examples of the basematerial include, for example, a glass. By using the base material, itis facilitated to form the S—H bond on the surface of the base materialby the pretreatment.

Therefore, in a preferable embodiment, the present invention alsoprovides:

a method for forming a surface-treating layer on a surface of a basematerial having a network structure of Si and O at least on its surfacecomprising the steps of

performing a pretreatment so as to form a Si—H bond on the surface ofthe base material; and

applying the surface-treating agent comprising the fluorine-containingcompound having a carbon-carbon unsaturated bond at its molecularterminal to the base material subjected to the pretreatment to form thesurface-treating layer on the surface of the base material; and

a process for producing an article comprising a base material and asurface-treating layer coating a surface of the base material comprisinga step of:

contacting the surface-treating agent of the present invention to thesurface of the base material so that the fluorine-containing compoundhaving a carbon-carbon unsaturated bond at its molecular terminalcontained in the surface-treating agent is reacted with a Si—H part or aC—H part of the surface of the base material to form thesurface-treating layer on the surface of the base material.

Since the surface-treating agent of the present invention contains thefluorine-containing compound having a carbon-carbon unsaturated bond atthe molecular terminal, the surface-treating agent of the presentinvention can form the surface-treating layer as long as the bindingsite with carbon-carbon unsaturated bond is present in the surface ofthe base material. Therefore, the pretreatment has only to be able toform the Si—H bond on the surface of the base material. For example, ahydrogen atom treatment or a thermal treatment under hydrogenatmosphere, described below, may be performed as the pretreatment.

Hydrogen Atom Treatment

A hydrogen gas of about 1×10⁻⁴ Pa is supplied to a vacuum chamber havingultra-high vacuum (not more than 1×10⁻⁶ Pa). The hydrogen molecular iscleaved by thermal electrons or plasma into hydrogen atoms, and thehydrogen atom is absorbed on the surface of the base material.

Thermal Treatment Under Hydrogen Atmosphere

Hydrogen vacuum condition (in particular, hydrogen atmosphere of notmore than 10⁻⁶ Pa) is made by flowing hydrogen as a carrier gas duringvacuum drawing to substitute the atmosphere of the chamber with thehydrogen gas. Hydrogen is absorbed on the surface of the base materialby heating the base material is heated to about 100-400° C. under theabove atmosphere.

By using the method for forming the surface-treating layer or theapparatus for forming the surface-treating layer, an organic monolayer,preferably a self-assembled monolayer can be formed as thesurface-treating layer on the surface of the base material.

In another embodiment, instead of the above pretreatment, a layer havingthe Si—H bond or the C—H bond may be formed on surface of the basematerial. For example, by forming a silicon dioxide on the surface ofthe base material, and performing the plasma treatment as describedabove, or by forming a diamond-like carbon layer, the layer having theSi—H bond or the C—H bond can be formed on the surface of the basematerial.

As described above, the surface-treating layer derived from the film ofthe surface-treating agent of the present invention is formed on thesurface of the base material to produce the article of the presentinvention.

Therefore, the article of the present invention comprises a basematerial and a layer which is formed on a surface of the base materialfrom the surface-treating agent (the surface-treating layer).

The present invention provides also a process for producing an articlecomprising a base material and a surface-treating layer coating asurface of the base material comprising a step of:

contacting the surface-treating agent of the present invention to thesurface of the base material so that the fluorine-containing compoundhaving a carbon-carbon unsaturated bond at its molecular terminalcontained in the surface-treating agent is reacted with a Si—H part or aC—H part of the surface of the base material to form thesurface-treating layer on the surface of the base material.

Since the surface-treating layer obtained by the present inventiondescribed above is bonded to the base material by the Si—C bond or theC—C bond, the surface-treating layer has high resistance to alkaline andultraviolet in addition to high physical strength. In addition, thesurface-treating layer obtained by the present invention may havewater-repellency, oil-repellency, antifouling property (for example,preventing from adhering a fouling such as fingerprints), surface slipproperty (or lubricity, for example, wiping property of a fouling suchas fingerprints and excellent tactile feeling in a finger) depending ona composition of the surface-treating agent used, thus may be suitablyused as a functional thin film.

Therefore, the present invention further provides an optical materialhaving the hardened material on the outermost layer.

Examples of the optical material include preferably a variety of opticalmaterials in addition to the optical material for displays, or the likeexemplified in below: for example, displays such as a cathode ray tube(CRT; for example, TV, personal computer monitor), a liquid crystaldisplay, a plasma display, an organic EL display, an inorganic thin-filmEL dot matrix display, a rear projection display, a vacuum fluorescentdisplay (VFD), a field emission display (FED; Field Emission Display),or a protective plate of such displays, or that in which these displaysand protective plates have been subjected to antireflection treatment ontheir surface.

The article having the surface-treating layer obtained according to thepresent invention is not specifically limited to, but may be an opticalmember. Examples of the optical member include the followings: lens ofglasses, or the like; a front surface protective plate, anantireflection plate, a polarizing plate, or an anti-glare plate on adisplay such as PDP and LCD; a touch panel sheet of an instrument suchas a mobile phone or a personal digital assistance; a disk surface of anoptical disk such as a Blu-ray disk, a DVD disk, a CD-R or MO; anoptical fiber; a display surface of a watch, and the like.

The article having the surface-treating layer obtained according to thepresent invention may be also a medical equipment or a medical material.

The thickness of the surface-treating layer is not specifically limited.For the optical member, the thickness of the surface-treating layer iswithin the range of 1-50 nm, 1-30 nm, preferably 1-15 nm, in view ofoptical performance, surface slip property, friction durability andantifouling property.

S Hereinbefore, the article produced by using the surface-treating agentof the present invention is described in detail. It is noted that anapplication, a method for using or a method for producing the articleare not limited to the above exemplification.

Example 1

Formation of surface-treating layer A glass was prepared as the basematerial, and the surface of the glass was plasma-treated to form theSi—H bond on the surface of the glass. The surface-treating layer wasformed on the surface of the glass treated by using the surface-treatingagent containing a fluorine-containing compound having the followingaverage composition by vacuum deposition under the following condition.

Fluorine-containing compound:

CF₃CF₂CF₂O(CF₂CF₂CF₂O)_(n)CF₂CF₂OCH₂CH═CH₂

wherein n is an integer of 20.

Vacuum Deposition Conditions

Equipment vacuum level: 1E-5 Pa

Temperature of the compound at the time of deposition: 200° C.

Temperature of the base material: room temperature (not controlled)

Deposition time: 10 minutes

After the vacuum deposition, the formation of CF_(x) layer was confirmedbased on the observation of orbital energy spectrum of C1s of thesurface-treating layer by using X-ray photoelectron spectroscopy (XPS).In addition, the static water contact angle of the surface-treatinglayer was measured for 5 μL of water at 25° C. by using a contact anglemeasuring instrument (manufactured by KYOWA INTERFACE SCIENCE Co.,Ltd.). The result was not less than 110°.

Examination Example 1 (Alkali Resistance Test)

An aqueous alkaline solution (25 wt % of aqueous KOH solution at pH 14)was added dropwise on the surface of the glass on which thesurface-treating layer formed as described above, and then the glass wasallowed to stand for 30 minutes. Then, the surface-treating layer wasobserved by using a XPS analysis. Chemical changes in thesurface-treating layer could not be observed 30 minutes after the addingdropwise of the aqueous alkaline solution since a peak shift of C1sorbital was changed. In addition, the static water contact angle wasmeasured as described above. The result was not less than 110°.

Examination Example 2 (Artificial Perspiration Test)

An alkaline artificial perspiration defined in JIS L 0848 “Test methodfor color fastness to perspiration” was added dropwise on the surface ofthe glass on which the surface-treating layer formed as described above,and then the glass was allowed to stand for 2 hours. Then, a thicknessof the surface-treating layer was measured by using an ellipsometer. Thethickness change before and after the adding dropwise of the artificialperspiration was not more than 1 nm, thus, deterioration of the layer bythe perspiration was not observed.

In addition, the surface-treating layers before and after the addingdropwise was observed by using a XPS analysis. Chemical changes in thesurface-treating layer could not be observed 2 hours after the addingdropwise of the artificial perspiration since a peak shift of C1sorbital was changed. In addition, the static water contact angle wasmeasured as described above. The result was not less than 110°.

From the above results, it was confirmed that the surface-treating layerhaving high alkali resistance and high perspiration resistance can beformed by using the surface-treating agent of the present invention.

INDUSTRIAL APPLICABILITY

The present invention can be suitably used for forming thesurface-treating layer on a surface of a base material, in particular anoptical member.

EXPLANATION OF THE REFERENCE NUMERALS

-   100: surface-treating layer forming apparatus-   200: pretreatment unit-   300: surface-treating layer forming unit-   400: base material transporting unit-   500: base material importing and exporting unit-   600: control unit-   201: chamber-   202: base material holder-   203: plasma generating unit-   204: exhaust mechanism-   211: importing and exporting port-   212: gate valve-   213: exhaust pipe-   214: pressure adjustment valve-   215: vacuum pump-   220: base material

The invention claimed is:
 1. A surface-treating agent for treating aglass base material having a Si—H bond on a surface of the glass basematerial, comprising a fluorine-containing compound having acarbon-carbon unsaturated bond at its molecular terminal and afluorine-containing oil which is one or more compounds of the formula(3):Rf¹—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—RF²  (3) wherein:Rf¹ is an alkyl group having 1-16 carbon atoms which may be substitutedby one or more fluorine atoms; Rf² is an alkyl group having 1-16 carbonatoms which may be substituted by one or more fluorine atoms, a fluorineatom or a hydrogen atom; a′, b′, c′ and d′ are the repeating number ofeach of four repeating units of perfluoro(poly)ether which constitute amain backbone of the polymer, and are each independently an integer of 0or more and 300 or less, the sum of a′, b′, c′ and d′ is 1 or more, andthe occurrence order of the respective repeating units in parentheseswith the subscript a′, b′, c′ and d′ is not limited in the formula,wherein the fluorine-containing compound having a carbon-carbonunsaturated bond at its molecular terminal is at least one compound ofany of the following formulae (A1), (A2), (B2), (C1), (C2), (D1) and(D2):

wherein: A is each independently at each occurrence —CH═CH₂ or —C≡CH; Yis a single bond; Rf is each independently an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;PFPE is each independently—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—, wherein a, b, c and dare each independently an integer of 0 or more and 200 or less, the sumof a, b, c and d is 1 or more, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula; R¹¹ is each independently a hydrogenatom or a halogen atom; R¹² is each independently at each occurrence ahydrogen atom or a lower alkyl group; X¹ is each independently a singlebond or a 2-10 valent organic group; X² is each independently at eachoccurrence a single bond or a divalent organic group; t is eachindependently an integer of 1-10; α is each independently an integer of1-9; α′ is each independently an integer of 1-9; X³ is eachindependently selected from the group consisting of:—(CH₂)₂—Si(CH₃)₂—(CH₂)₂— —CONH—(CH₂)₃—, —CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— (wherein Ph is a phenyl group), —CONH—(CH₂)₆—,—CON(CH₃)—(CH₂)₆—, —CON(Ph)-(CH₂)₆— (wherein Ph is a phenyl group),—CONH—(CH₂)₂NH(CH₂)₃—, —CONH—(CH₂)₆NH(CH₂)₃—, —CH₂O—CONH—(CH₂)₃—,—CH₂O—CONH—(CH₂)₆—, —S—(CH₂)₃—, —(CH₂)₂S(CH₂)₃—, —C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₆—, —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,

β is 1; X⁴ is each independently a single bond or a 2-10 valent organicgroup; γ is each independently an integer of 1-9; γ′ is eachindependently an integer of 1-9; R^(a) is each independently at eachoccurrence —Z—SiR⁷¹ _(p)R⁷² _(q)R⁷³ _(r)R⁷⁴ _(s); Z is eachindependently at each occurrence an oxygen atom or a divalent organicgroup; R⁷¹ is each independently at each occurrence R^(a′); R^(a′) hasthe same definition as that of R^(a); in R^(a), the number of Si atomswhich are straightly linked via the Z group is up to five; R⁷² is eachindependently at each occurrence —X⁵—Y-A; X⁵ is each independently ateach occurrence a single bond or a divalent organic group; R⁷³ is eachindependently at each occurrence a hydroxyl group or a hydrolyzablegroup; R⁷⁴ is each independently at each occurrence a hydrogen atom or alower alkyl group; p is each independently at each occurrence an integerof 0-3; q is each independently at each occurrence an integer of 0-3; ris each independently at each occurrence an integer of 0-3; s is eachindependently at each occurrence an integer of 0-3; with the provisothat (p+q+r+s) is 3; R^(b) is each independently at each occurrence—X⁵—Y-A; R^(c) is each independently at each occurrence a hydroxyl groupor a hydrolyzable group; R^(d) is each independently at each occurrencea hydrogen atom or a lower alkyl group; k is each independently at eachoccurrence an integer of 0-3; l is each independently at each occurrencean integer of 0-3; m is each independently at each occurrence an integerof 0-3; n is each independently at each occurrence an integer of 0-3;with the proviso that (k+l+m+n) is 3, and there is at least one the Y-Agroup in —(SiR^(a) _(k)R^(b) _(l)R^(c) _(m)R^(d) _(n))_(r); X⁶ is eachindependently a single bond or a 2-10 valent organic group; δ is eachindependently an integer of 1-9; δ′ is each independently an integer of1-9; R⁹¹ is a fluorine atom, —CHF₂ or —CF₃; and Rf′ is aperfluoroalkylene group having 1-20 carbon atoms, and thefluorine-containing compound can bind to the glass base material by aSi—C bond.
 2. The surface-treating agent according to claim 1 wherein Ais —CH═CH₂.
 3. The surface-treating agent according to claim 1 whereinRf is a perfluoroalkyl group having 1-16 carbon atoms.
 4. Thesurface-treating agent according to claim 1 wherein PFPE is a group ofany of the following formulae (a)-(c):—(OC₃F₆)_(b)—  (a) in the formula (a), b is an integer of 1 or more and200 or less;—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄—(OCF₂)_(d)—  (b) in the formula (b), aand b is each independently an integer of 0 or more and 30 or less, cand d is each independently an integer of 1 or more and 200 or less, thesum of a, b, c and d is an integer of 10 or more and 200 or less, andthe occurrence order of the respective repeating units in parentheseswith the subscript a, b, c or d is not limited in the formula, and—(OC₂F₄—R¹⁵)_(n″)—  (c) in the formula (c), R¹⁵ is each independently agroup selected from OC₂F₄, OC₃F₆ and OC₄F₈, and n″ is an integer of2-100.
 5. The surface-treating agent according to claim 1 wherein inPFPE: OC₄F₈ is OCF₂CF₂CF₂CF₂, OC₃F₆ is OCF₂CF₂CF₂, and OC₂F₄ is OCF₂CF₂.6. The surface-treating agent according to claim 1 wherein X¹, X⁴ and X⁶are a 2-4 valent organic group, α, γ and δ are 1-3, and α′, γ′ and δ′are
 1. 7. The surface-treating agent according claim 1 wherein X¹, X⁴and X⁶ are a divalent organic group, α, γ and δ are 1, and α′, γ′ and δ′are
 1. 8. The surface-treating agent according to claim 1 wherein X¹, X⁴and X⁶ are each independently —(R³¹)_(p′)—(X^(a))_(q′)—R³²— wherein: R³¹is a single bond, —(CH₂)_(s′)— (wherein s′ is an integer of 1-20) or ano-, m- or p-phenylene group; R³² is a single bond, —(CH₂)_(t′)— (whereint′ is an integer of 1-20) or an o-, m- or p-phenylene group; X^(a) is—(X^(b))_(r′)— (wherein r′ is an integer of 1-10); X^(b) is eachindependently at each occurrence a group selected from the groupconsisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—,—CONR³⁴—, —O—CONR³⁴—, —NR³⁴— and —(CH₂)_(n′)— (wherein n′ is an integerof 1-20); R³³ is each independently at each occurrence a phenyl group, aC₁₋₆alkyl group or a C₁₋₆alkoxy group; R³⁴ is each independently at eachoccurrence a hydrogen atom, a phenyl group or a C₁₋₆alkyl group; p′ is 0or 1; q′ is 0 or 1; at least one of p′ and q′ is 1, the occurrence orderof the respective repeating units in parentheses with the subscript p′or q′ is not limited in the formula; and R³¹, R³² and X^(a) may besubstituted with one or more substituents selected from a fluorine atom,a C₁₋₃alkyl group and a C₁₋₃fluoroalkyl group.
 9. The surface-treatingagent according to claim 1 wherein X¹, X⁴ and X⁶ are each independentlyselected from the group consisting of: —CH₂O(CH₂)₂—, —CH₂O(CH₂)₃—,—CH₂O(CH₂)₆—, —CH₂OCF₂CHFOCF₂—, —CH₂OCF₂CHFOCF₂CF₂—,—CH₂OCF₂CHFOCF₂CF₂CF₂—, —CH₂OCH₂CF₂CF₂OCF₂—, —CH₂OCH₂CF₂CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—, —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—, —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂—, —CH₂OCH₂CHFCF₂OCF₂CF₂—, —CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—, —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂— —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₆—, —(CH₂)₂—Si(CH₃)₂—(CH₂)₂— —CONH—(CH₂)₃—, —CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— (wherein Ph is a phenyl group), —CONH—(CH₂)₆—,—CON(CH₃)—(CH₂)₆—, —CON(Ph)-(CH₂)₆— (wherein Ph is a phenyl group),—CONH—(CH₂)₂NH(CH₂)₃—, —CONH—(CH₂)₆NH(CH₂)₃—, —CH₂O—CONH—(CH₂)₃—,—CH₂O—CONH—(CH₂)₆—, —S—(CH₂)₃—, —(CH₂)₂S(CH₂)₃—, —C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₆—, —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,


10. The surface-treating agent according to claim 1 wherein X¹ is—O—CFR¹³—(CF₂)_(e)—, R¹³ is a fluorine atom or a lower fluoroalkylgroup, and e is 0 or
 1. 11. The surface-treating agent according toclaim 1 wherein X² is —(CH₂)_(u)—, and u is an integer of 0-2.
 12. Thesurface-treating agent according to claim 1 wherein R⁹¹ is a fluorineatom or CF₃.
 13. The surface-treating agent according to claim 1 whereinthe fluorine-containing compound having a carbon-carbon unsaturated bondat its molecular terminal is at least one compound of any of theformulae (A1) and (A2).
 14. The surface-treating agent according toclaim 1 wherein the fluorine-containing compound having a carbon-carbonunsaturated bond at its molecular terminal is at least one compound ofthe formula (B2).
 15. The surface-treating agent according to claim 1wherein the fluorine-containing compound having a carbon-carbonunsaturated bond at its molecular terminal is at least one compound ofany of the formulae (C1) and (C2).
 16. The surface-treating agentaccording to claim 1 wherein the fluorine-containing compound having acarbon-carbon unsaturated bond at its molecular terminal is at least onecompound of any of the formulae (D1) and (D2).
 17. The surface-treatingagent according to claim 1 further comprising one or more componentsselected form a silicone oil, and a catalyst.
 18. The surface-treatingagent according to claim 1 wherein the fluorine-containing oil is one ormore compounds of the formula (3a) or (3b):Rf¹—(OCF₂CF₂CF₂)_(b″)—Rf²  (3a)Rf¹—(OCF₂CF₂CF₂CF₂)_(a″)—(OCF₂CF₂CF₂)_(b″)—(OCF₂CF₂)_(c″)—(OCF₂)_(d″)—Rf²  (3b)wherein: Rf¹ is an alkyl group having 1-16 carbon atoms which may besubstituted by one or more fluorine atoms; Rf² is an alkyl group having1-16 carbon atoms which may be substituted by one or more fluorineatoms, a fluorine atom or a hydrogen atom; in the formula (3a), b″ is aninteger of 1 or more and 100 or less; in the formula (3b), a″ and b″ areeach independently an integer of 0 or more and 30 or less, and c″ and d″are each independently an integer of 1 or more and 300 or less; and theoccurrence order of the respective repeating units in parentheses withthe subscript a″, b″, c″ or d″ is not limited in the formula.
 19. Thesurface-treating agent according to claim 1 further comprising asolvent.
 20. The surface-treating agent according to claim 1 which canbe used as an antifouling-coating agent or a water-proof coating agent.21. An article comprising a glass base material and a layer which isformed on a surface of the base material from the surface-treating agentaccording to claim
 1. 22. The article according to claim 21 wherein theglass is a glass selected from the group consisting of a soda-limeglass, an alkali aluminosilicate glass, a borosilicate glass, anon-alkaline glass, a crystal glass and a quartz glass.
 23. The articleaccording to claim 21 which is an optical member.
 24. A method forforming a surface-treating layer on a surface of a glass base materialcomprising the steps of: performing a pretreatment of the base materialso as to form a Si—H bond as a binding site with a fluorine-containingcompound having a carbon-carbon unsaturated bond at its molecularterminal on the surface of the base material; and applying thesurface-treating agent according to claim 1 to the base materialsubjected to the pretreatment to form the surface-treating layer on thesurface of the base material.
 25. The method for forming asurface-treating layer according to claim 24 wherein in thepretreatment, an amount of H and an amount of O on the surface of thebase material are controlled with a plasma containing hydrogen dependingon the surface-treating agent used.
 26. The method for forming asurface-treating layer according to claim 24 wherein the pretreatment isperformed by using the plasma containing hydrogen, and a Si—H bondhaving a function as the binding site with the fluorine-containingcompound having a carbon-carbon unsaturated bond at its molecularterminal is formed on the surface of the base material by the plasma.27. The method for forming a surface-treating layer according to claim24 wherein the pretreatment is performed by using the plasma containinghydrogen.
 28. The method for forming a surface-treating layer accordingto claim 24 wherein the pretreatment is performed by using a hydrogenand rare gas plasma or a hydrogen plasma.
 29. The method for forming asurface-treating layer according to claim 24 wherein in thepretreatment, a hydrogen gas is supplied into a chamber held in a vacuumstate, the hydrogen gas is cleaved to hydrogen atoms with a thermoelectron or the plasma, and the hydrogen atoms are absorbed on thesurface of the base material in the chamber.
 30. The method for forminga surface-treating layer according to claim 24 wherein in thepretreatment, a chamber is brought to a vacuum state under a hydrogenatmosphere, and the base material is heated in the chamber so that thehydrogen atom is absorbed on the surface of the base material.
 31. Themethod for forming a surface-treating layer according claim 24 whereinthe surface-treating layer is an organic monolayer.
 32. The method forforming a surface-treating layer according to claim 24 wherein thesurface-treating layer is a self-assembled monolayer.
 33. A process forproducing an article comprising a base glass material having a Si—H bondon the surface of the base glass material and a surface-treating layercoating the surface of the base material comprising a step of:contacting the surface-treating agent according to claim 1 to thesurface of the base material so that the fluorine-containing compoundhaving a carbon-carbon unsaturated bond at its molecular terminalcontained in the surface-treating agent is reacted with a Si—H part ofthe surface of the base material to form the surface-treating layer onthe surface of the base material.
 34. The process for producingaccording to claim 33 further comprising performing a pretreatment ofthe base glass material so as to form the Si—H bond as a binding sitewith the fluorine-containing compound having a carbon-carbon unsaturatedbond at its molecular terminal on the surface of the base glassmaterial.
 35. The process for producing according to claim 33 whereinthe Si—H bond is introduced on the surface of the base material byforming a layer having the Si—H.